Synthesis, structure, and properties of [(tmeda)Cu[Hg(CN)2]2][HgCl4]: A non-centrosymmetric 2-D layered system that shows strong optical anisotropy

Neil D. Draper; Raymond J. Batchelor; Bryan C. Sih; Zuo Guang Ye; Daniel B. Leznoff

doi:10.1021/cm021716r

Synthesis, structure, and properties of [(tmeda)Cu[Hg(CN)₂]₂][HgCl₄]: A non-centrosymmetric 2-D layered system that shows strong optical anisotropy

Neil D. Draper
, Raymond J. Batchelor
, Bryan C. Sih
, Zuo Guang Ye
, Daniel B. Leznoff

Simon Fraser University

Research output: Contribution to journal › Article › peer-review

28 Scopus citations

Abstract

The first coordination polymer incorporating Hg(CN)₂ units as building blocks is reported. The reaction of the labile transition-metal halide CuCl₂, the soft Lewis acidic Hg(CN)₂, and N,N,N′,N′-tetramethylethylenediamine (tmeda) formed large single crystals of [(tmeda)Cu[Hg(CN)₂]₂][HgCl₄] (1). The migration of two labile chloride ligands from harder Cu(II) to softer Hg(II) drives the formation of 1, which self-assembles in high yield from several combinations of reagents. Complex 1 crystallizes in the tetragonal, noncentric P42₁m space group, Z = 2, with a = b = 10.9576(12) Å and c = 9.8516(13) A. The structure is composed of a 2-D cationic layer of [(tmeda)Cu[Hg(CN)₂]₂]²⁺ units in which the six-coordinate Cu(II) centers are bridged by four Hg(CN)₂ groups and capped by a tmeda ligand. This array is interspersed with a layer of [HgCl₄]^2- anions, which form bridging Hg-Cl bonds with the Hg(CN)₂ units. At 300 K, a- or b-oriented single-crystal plates of 1 are strongly birefringent with a birefringence value of Δn = 6.38 × 10^-2, as measured at λ = 546.1 nm. The strongly anisotropic crystal structure, including the highly polarizable Hg(II) ions, is responsible for this significant optical birefringence. Upon cooling, the birefringence of 1 decreases slightly to Δn = 6.12 × 10^-2 at 90 K.

Original language	English
Pages (from-to)	1612-1616
Number of pages	5
Journal	Chemistry of Materials
Volume	15
Issue number	8
DOIs	https://doi.org/10.1021/cm021716r
State	Published - 22 Apr 2003
Externally published	Yes

Access to Document

10.1021/cm021716r

Cite this

@article{2e4e8eb3cbc144fea77402b6fb4425c2,

title = "Synthesis, structure, and properties of [(tmeda)Cu[Hg(CN)2]2][HgCl4]: A non-centrosymmetric 2-D layered system that shows strong optical anisotropy",

abstract = "The first coordination polymer incorporating Hg(CN)2 units as building blocks is reported. The reaction of the labile transition-metal halide CuCl2, the soft Lewis acidic Hg(CN)2, and N,N,N′,N′-tetramethylethylenediamine (tmeda) formed large single crystals of [(tmeda)Cu[Hg(CN)2]2][HgCl4] (1). The migration of two labile chloride ligands from harder Cu(II) to softer Hg(II) drives the formation of 1, which self-assembles in high yield from several combinations of reagents. Complex 1 crystallizes in the tetragonal, noncentric P421m space group, Z = 2, with a = b = 10.9576(12) {\AA} and c = 9.8516(13) A. The structure is composed of a 2-D cationic layer of [(tmeda)Cu[Hg(CN)2]2]2+ units in which the six-coordinate Cu(II) centers are bridged by four Hg(CN)2 groups and capped by a tmeda ligand. This array is interspersed with a layer of [HgCl4]2- anions, which form bridging Hg-Cl bonds with the Hg(CN)2 units. At 300 K, a- or b-oriented single-crystal plates of 1 are strongly birefringent with a birefringence value of Δn = 6.38 × 10-2, as measured at λ = 546.1 nm. The strongly anisotropic crystal structure, including the highly polarizable Hg(II) ions, is responsible for this significant optical birefringence. Upon cooling, the birefringence of 1 decreases slightly to Δn = 6.12 × 10-2 at 90 K.",

author = "Draper, \{Neil D.\} and Batchelor, \{Raymond J.\} and Sih, \{Bryan C.\} and Ye, \{Zuo Guang\} and Leznoff, \{Daniel B.\}",

year = "2003",

month = apr,

day = "22",

doi = "10.1021/cm021716r",

language = "英语",

volume = "15",

pages = "1612--1616",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

number = "8",

}

TY - JOUR

T1 - Synthesis, structure, and properties of [(tmeda)Cu[Hg(CN)2]2][HgCl4]

T2 - A non-centrosymmetric 2-D layered system that shows strong optical anisotropy

AU - Draper, Neil D.

AU - Batchelor, Raymond J.

AU - Sih, Bryan C.

AU - Ye, Zuo Guang

AU - Leznoff, Daniel B.

PY - 2003/4/22

Y1 - 2003/4/22

N2 - The first coordination polymer incorporating Hg(CN)2 units as building blocks is reported. The reaction of the labile transition-metal halide CuCl2, the soft Lewis acidic Hg(CN)2, and N,N,N′,N′-tetramethylethylenediamine (tmeda) formed large single crystals of [(tmeda)Cu[Hg(CN)2]2][HgCl4] (1). The migration of two labile chloride ligands from harder Cu(II) to softer Hg(II) drives the formation of 1, which self-assembles in high yield from several combinations of reagents. Complex 1 crystallizes in the tetragonal, noncentric P421m space group, Z = 2, with a = b = 10.9576(12) Å and c = 9.8516(13) A. The structure is composed of a 2-D cationic layer of [(tmeda)Cu[Hg(CN)2]2]2+ units in which the six-coordinate Cu(II) centers are bridged by four Hg(CN)2 groups and capped by a tmeda ligand. This array is interspersed with a layer of [HgCl4]2- anions, which form bridging Hg-Cl bonds with the Hg(CN)2 units. At 300 K, a- or b-oriented single-crystal plates of 1 are strongly birefringent with a birefringence value of Δn = 6.38 × 10-2, as measured at λ = 546.1 nm. The strongly anisotropic crystal structure, including the highly polarizable Hg(II) ions, is responsible for this significant optical birefringence. Upon cooling, the birefringence of 1 decreases slightly to Δn = 6.12 × 10-2 at 90 K.

AB - The first coordination polymer incorporating Hg(CN)2 units as building blocks is reported. The reaction of the labile transition-metal halide CuCl2, the soft Lewis acidic Hg(CN)2, and N,N,N′,N′-tetramethylethylenediamine (tmeda) formed large single crystals of [(tmeda)Cu[Hg(CN)2]2][HgCl4] (1). The migration of two labile chloride ligands from harder Cu(II) to softer Hg(II) drives the formation of 1, which self-assembles in high yield from several combinations of reagents. Complex 1 crystallizes in the tetragonal, noncentric P421m space group, Z = 2, with a = b = 10.9576(12) Å and c = 9.8516(13) A. The structure is composed of a 2-D cationic layer of [(tmeda)Cu[Hg(CN)2]2]2+ units in which the six-coordinate Cu(II) centers are bridged by four Hg(CN)2 groups and capped by a tmeda ligand. This array is interspersed with a layer of [HgCl4]2- anions, which form bridging Hg-Cl bonds with the Hg(CN)2 units. At 300 K, a- or b-oriented single-crystal plates of 1 are strongly birefringent with a birefringence value of Δn = 6.38 × 10-2, as measured at λ = 546.1 nm. The strongly anisotropic crystal structure, including the highly polarizable Hg(II) ions, is responsible for this significant optical birefringence. Upon cooling, the birefringence of 1 decreases slightly to Δn = 6.12 × 10-2 at 90 K.

UR - https://www.scopus.com/pages/publications/0037461244

U2 - 10.1021/cm021716r

DO - 10.1021/cm021716r

M3 - 文章

AN - SCOPUS:0037461244

SN - 0897-4756

VL - 15

SP - 1612

EP - 1616

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 8

ER -

Synthesis, structure, and properties of [(tmeda)Cu[Hg(CN)₂]₂][HgCl₄]: A non-centrosymmetric 2-D layered system that shows strong optical anisotropy

Abstract

Access to Document

Other files and links

Fingerprint

Cite this